Production of nonionic detergents from oxidized wax and olefin oxide



Patented Feb. 20, 195E PRODUCTION OF NONIONIG DETERGENTS FROM OXIDIZED WAX AND OLEFKN OXIDE John a. Nevison, Media, and William K. Grie singer, Drexel Hill, Pa., assignors to The Atlantic Refining Company, Philadelphia, Pa.,

ration of Pennsylvania No Drawing.

a corpo- Serial No. 133,478

The present invention relates to the production 01: non-ionic detergents by subjecting hydrocarbon wax to oxidation, reacting the entire oxidation mixture including unoxidized wax with an 5 Claims. (Cl. 260-410-62 Application December 16, 1949,

unoxygenated wax, with or without removal of the oxidation catalyst, is heated to a temperature within the range of 350 F. to 450 F., and preferably 375 F. to 425 F. To the mixture is olefin oxide to convert the oxidized wax compo- 5 added a condensation catalyst, for example, 1% nents into water-soluble, oxygenated products. by weight of sodium glycerophosphate and and separating these products from the unoxiby weight of dry sodium hydroxide pellets based dized wax. upon the total amount of oxidized wax acids A further object of the invention is to increase present. The amount of sodium hydroxide may the yield and enhance the detergent properties 10 vary between 5% and and catalysts other of the product by returning separated, unoxidized than the specific combination above mentioned wax to the initial oxidation process. may be used. An olefin oxide, such as ethylene. A Iurther object of the invention is to improve oxide, is then introduced into the heated mixthe detergent product by dissolution in an aroture, and the condensation reaction proceeds. In matic hydrocarbon solvent and separation of in- 15 order to obtain water-soluble products, ethylene soluble impurities. oxide in'the amount of 10 to equivalents is In accordance with this invention, a hydrocaradmitted during the reaction period, which is bon wax, preferably a paraflin wax melting beusually of the order or 8 to 15 hours, a period of tween 45 F. and 150 F. is subjected to oxidation about 10 hours being average. The ethylene with air or other gaseous oxidizing medium in 20 oxide equivalent is determined in the following the presence of an oxidation catalyst at a temmanner. perature between 230 F. and 400 F., and prefer- A representative sample of the oxidized wax ably between 260 F. and 300 F. forsuflicient mixture is saponified with excess aqueous sodium time to convert a substantial proportion of the hydroxide solution. The resulting aqueous soluwax into oxygenated compounds such as cartion of sodium salts of the oxidized wax acids is boxylic acids, esters. and aldehydes. The averextracted with petroleum naphtha to remove unage carbon atom content of the wax preferably oxidized wax, and the aqueous solution is acidiranges between 15 and 30, and the carbon atom fled with mineral acid to liberate the wax acids. content of the oxygenated product is preferably the weight of which is noted. The wax acids are of the order of 12 to 14. A charge wax of an then titrated with alcoholic potassium hydroxide average 01 15 carbon atoms will give oxygenated to the phenolphthalein endpoint and the saponiproducts of about 10 carbon atoms, and a charge flcation number thus obtained. From the sawax of 30 carbon atoms will give products of poiilfication number, the molecular weight of the about 18 carbon atoms. The oxidation may be wax acids is calculated. From this data, the conducted at atmospheric or super-atmospheric ethylene oxide equivalent is obtained from the pressures, using oxidation catalysts such as poiollowing relationship:

Equh-rr (Wt. of Oxid. Mix) my Acids/100) (M01. Wt. of Eth. Oxide) tassium permanganate, manganese stearate or naphthenate, cobalt stearate or naphthenate in small amounts, i. e., 0.1 %-0.5% by weight, preferably in the presence of a small amount of a base, e. g., 0.1%-0.5% of sodium carbonate to reduce the formation of hydroxy acids. The oxidation period usually ranges from 10 to 30 hours depending upon the nature of the wax, the amount of air and the temperature employed. For example, using a 90 F. melting point paraflln wax, an oxidation period of 18 to 22 hours is preferred, the temperature being about 300 F.. the catalyst 0.1% manganese naphthenate and 0.1% sodium carbonate, and the air rate about 3 cc. per minute per gram of wax charge. However, the air rate may be varied within the range of 1 to 6 cc. per minute, but a rate of 2 to 3 cc. per minute is preferred.

Upon completion 0! the oxidation step, the entire mixture of oxygenated wax components and (M01. Wt. of Wax Acids Upon completion of the condensation reaction between the ethylene oxide and the oxygenated components of the wax, the entire mixture of water-soluble condensation product and unoxidized wax is permitted to stand, whereupon the catalyst settles as a separate phase and is removed. The mixture is then cooled and treated with several volumes of liquid paraflinic hydrocarbon such as pentane, hexane, petroleum ether, or petroleum naphtha boiling within the range of F. to 400 F. Such treatment may be carried out by diluting or washing the reaction mixture with 3 or 4 volumes of liquid paraflinic hydrocarbon (100% by volume each based upon the volume of reaction mixture). As a result of this treatment, the unoxidized wax is dissolved and removed from the water-soluble, oxygenated condensation product. The solution of unoxidized wax may be distilled to recover the paraflinic hydrocarbon and the residue of unoxidized wax may be returned to the initial oxidation step, in admixture with fresh wax, for conversion into oxygenated wax. Residual paraflinic hydrocarbon may be removed from the water-soluble condensation product by vaporization at reduced pressure, preferably with moderate heating. In many cases, it has been found that the watersoluble oxygenated condensation product, upon standing for a period of time, will deposit a sediment which comprises primarily finely divided catalyst. To remove this material from the condensation product immediately following the condensation reaction and separation of unoxidized wax, the condensation product may be diluted with 2 to 4 volumes of an aromatic hydrocarbon solvent such as benzene, toluene, xylene, cumene, or the like, preferably boiling below 400 F. The condensation product is dissolved in the aromatic'solvent, and the solid impurities, e. g., catalyst, may be settled out or removed by filtration. The aromatic solvent may be recovered from the purified product by vaporization, preferably under reduced pressure.

The non-ionic detergents produced from a once-through operation are usually amber to reddish colored liquids which possess pleasant ester-like odor, while those produced by repeated recycling of separated, unoxidized wax to the initial oxidation step are brown, viscous to solid materials. These non-ionic detergents may be admixed with various amounts of inorganic salts such as alkali metal sulfates, pyrophosphates, polyphosphates (particularly tripolyphosphates), carbonates, or mixtures of two or more thereof, to obtain improved detergency or synergistic properties. Also, the detergents produced in accordance with this invention may be admixed with cationic or anionic detergents or soaps including alkyl sulfates or sulfated higher alcohols, aryl sulfonates, allql aryl sulfonates especially those containing 12 to 15 carbon atoms in the alkyl group, alkyl phenol sulfonates, alkyl naphthalene sulfonates, alkanolamine soaps of sulfonic acids and of fatty acids, alkali metal soaps of fatty acids, and the like.

The present invention may be further illustrated by the following examples, which, however, are not to be construed as limiting the scope thereof.

(1) A 90 F. melting point paraffin wax was oxidized at 300 F. for 16 hours using a catalyst golnysisting of 0.1% manganese naphthenate and I through the mixture at a rateof 3 cc. per gram of wax per minute. Following the oxidation step, the mixture was divided in a plurality of samples, each being heated to 400 F. and ethylene oxide introduced in a different amount for a period of hours, employing in each case a condensation catalyst of 1% sodium glycerophosphate and 10% caustic soda. Each of the condensation reaction mixtures, i. e., water-soluble product and unreacted wax, was washed with 4 volumes of 88 paraffinic petroleum naphtha to remove unreacted wax. The resulting non-ionic detergents were each mixed with sodium sulfate to give mixtures of 40% detergent-% sodium sulfate. These mixtures were tested for cotton detergency by a standard Launderometer test at concentrations of 0.3% and.0.5% in tap water. The results are shown in the following table.

Carbon atom Detergcncy content of Eth. Oxide war acids Equival.

(av.) 0.3% cone. 0.5% cone.

l6 l0 15 40 16 12.6 24 32 16 15. 6 60 64 16 l. 4 58 69 16 21. 7 47 01 (2) A paraflin wax having a melting point of 90 F., a boiling range of 360 F. to 401 F., and a molecular weight of 274 was oxidized with air in the presence of a manganese naphthenatesodium carbonate catalyst, the resulting mixture of oxygenated and unoxidized wax was condensed with ethylene oxide in the presence of sodium glycerophosphate caustic soda catalyst, the water-soluble oxygenated condensation product was washed with pentane to remove unoxidized wax, and the condensation product in the crude state, as well as after purification with benzene, was tested for detergency in concentrations of 0.3% and 0.5% in a standard Launderometer test. After removal of pentane from the unoxidized wax, such wax was recycled with fresh wax to the oxidation step. This operation was repeated through 4 runs, the results of which are tabulated below.

Oxidation step Charge, g. Oxidation Products E 9 H Air un ernp. ours Fresh Re- F. Wt. Acid Sap, EE? cycle g. No. No. g

l 375 0 320 22 3.2 362 99 202 40 2 157 218 320 22 3. Z 364 14 92 20 3 85 290 320 22 3.2 363 34 92 20 4 at 320 320 22 3.2 354 20 mi 20 Condensation step Eth. Ox- Recov. Wax Non-ionic Detergent idc added (xaahilyst,

ercent Run t'ii NGP, Refined E Igzrcegt Acid Sap Crude, 1;. q. 2.0 No No. g. 2 Acid sap. No. No.

1- 331 .9 400 M 230 0 475 413 1.3 6i 2...... 166 11.8 400 M1 306 0 30 259 216 0 36 3... 164 11.8 400 $6 338 0 37 200 1% 0 415 4.-." 16" 12.0 400 H1 292 0 20 235 217 0 38 sodium carbonate, with bubbling air Non-ionic detergent Detergency "was me IQOO mm asreiined ionic/I P 123 non-ionic partswax m 0.3 0.5% 03% 0.5%

34 35 34 as as 112 m 41 .60 4a 04 as as as as 70 e1 ill 49 21c 70 75 as -73 as as 394 From the description and data given herein, it will be apparent that a simple and economic method is provided for producing non-ionic detergents by the direct condensation of an olefln oxide with the oxygenated components of hydrocarbon wax, and the direct recovery of the condensation product from the unoxidized wax. Such method avoids the difliculties and expense involved in prior art methods wherein the oxygenated wax components were first recovered by saponification and acidification. and thereafter, with or without fractional distillation. condensed with olefin oxides.

We claim:

1. A method oi producing a non-ionic deter-.

gent, which comprises reacting a mixture containing oxygenated and unoxygenated hydrocarbon wax with sumcient ethylene oxide such that the oxygenated reaction product is water-soluble, treating the reaction mixture containing the oxygenated, water-soluble product and unoxygenated hydrocarbon wax with sumcient liquid paraflinic hydrocarbon to dissolve the unoxygenated hydrocarbon wax but not the oxygenated. water-soluble product, and separating the solution of liquid paraflinic hydrocarbon and unoxygenated wax from the oxygenated, water-soluble product.

taining oxygenated and unoxygenated hydrocarbon wax with to equivalents of ethylene oxide at 375 F. to 425 F., treating the reaction mixture containing the oxygenated water-soluble product and unoxygenated hydrocarbon wax with -8uiilcient liquid paramnic hydrocarbon boiling between 100' F. and 400 F. to dissolve the unoxygenated hydrocarbon wax but not the oxygenated, water-soluble product, and separating the liquid paraillnic hydrocarbon and unoxygenated wax from the oxygenated, water-soluble product.

4. A method oi producing a non-ionic detergent. which comprises reacting a mixture containing oxygenated and unoxygenated hydrocarbon wax with 10 to 15 equivalents of ethylene oxide at 375 F. to 425 F., treating the reaction mixture containing the oxygenated, water-soluble product and unoxygenated hydrocarbon wax with suiiicient liquid paraflinic hydrocarbon boiling between F. and 400 1". to dissolve the unoxygenated hydrocarbon wax but not the oxygenated, water-soluble product. separating the 2. A method of producing a non-ionic detergent, which comprises reacting a mixture conliquid paraflinic hydrocarbon and unoxygenated wax from the oxygenated, water-soluble product. dissolving the oxygenated, water-soluble product in a liquid aromatic hydrocarbon solvent, separating the resultant solution from insoluble impurities. and removing the aromatic hydrocarbon solvent from the purified product.

5. Amethodaccordingtoclaimainwhichthe liquid paramnic hydrocarbon is pentane and the aromatic hydrocarbon solvent is benzene.

JOHN A. NEVISON. WIILIAH K. GRIBSINGER.

088 mm Theiollowingreierencesareoirecordinthe ills of this patent:

UNITED STATES PATENTS Number Name Date 2,283,382 De Groote l'bb. 25,1941 

1. A METHOD OF PRODUCING A NON-IONIC DETERGENT, WHICH COMPRISES REACTING A MIXTURE CONTAINING OXYGENATED AND UNOXYGENATED HYDROCARBON WAX WITH SUFFICIENT ETHYLENE OXIDE SUCH THAT THE OXYGENATED REACTION PRODUCT IS WATER-SOLUBLE, TREATING THE REACTION MIXTURE CONTAINING THE OXYGENATED, WATER-SOLUBLE PRODUCT AND UNOXYGENATED HYDROCARBON WAX WITH SUFFICIENT LIQUID PARAFFINIC HYDROCARBON TO DISSOLVE THE UNOXYGENATED HYDROCARBON WAX BUT NOT THE OXYGENATED, WATER-SOLUBLE PRODUCT, AND SEPARATING THE SOLUTION OF LIQUID PARAFFINIC HYDROCARBON AND UNOXYGENERATED WAX FROM THE OXYGENATED, WATER-SOLUBLE PRODUCT. 